Process for the manufacture of aminoanthraquinones

ABSTRACT

Process for the preparation of anthraquinones containing a primary amino group by heating the corresponding aminoanthraquinones containing a secondary or tertiary amino group in an organic solvent.

United States Patent Altermatt Oct. 24, 1972 [s41 PROCESS FOR THE MANUFACTURE 51] rm. (:1. ..C09b 1/22 0F AMINOANTHRAQUINONES [58] Field of Search ..260/377, 378, 380, 381 [72] Inventor: Hans Altermatt, Reinach, Basel- Land Switzerland [56] References Cited [73] Assignee: Ciba-Geigy AG, Basel, Switzerland UNITED STATES PATENTS D Braun et al. [21] Appl. No.: 883,343 Pr imary Examiner-Lorraine A. Weinberger Assistant ExaminerE. Jane Skelly Related Apphcanon Dam Att0rney-Harry Goldsmith, Joseph G. Kolodny and [63] Continuation-impart Of Ser. NO 631,879, April Mari" 9, l 1967 abandoned ABSTRACT [30] Foreign Application Priority Data, Process for the preparation of anthraquinones con- .taining a primary amino group by heating the cor- May 11, 1966 Switzerland ..6880/66 responding aminoamhraquinones containing a Secon l t. 52 us. Cl. ..260/371, 260/329.2, 260/377, dary ternary ammo group m an ("game so 260/378, 260/380, 260/381 15 Claims, No Drawings acid or oleum are used, nitrile groups or amide groups may at the same time be saponified or sulphonic acid groups may be simultaneously introduced. In the above-mentioned Specification the advantages compared with earlier known processes of manufacture are also mentioned, especially the process of converting N- substituted sulphonic acid amides, especially N-substituted p-toluenesulphonic acid amides, into amines by hydrolysis with strong acids, for example sulphuric or hydrochloric acid. Thus for example cyclohexylarnino compounds are not, like the arylsulphonamide compounds, only accessible from halogen compounds but' also from other compounds having negative substituents, for example sulphonic acids or nitro compounds, by reacting these with cyclohexylamine, so that according to the new amine synthesis a far larger number of starting substances can be converted to the corresponding amines. Furthermore, in compounds containing several negative substituents of equal reactivity, such as are for example present in 1,4- or 1,5- dichloranthraquinone, it is possible, if desired, to react only one of these groups with cyclohexylamine and thus after the conversion, to obtain aminohalogenanthraquinones or the corresponding sulphonic acids. This clearly defined exchange of only one of the chlorine atoms in dichloranthraquinones is not possible with toluenesulphonamide, since in most cases a mixture of monotosylamino and ditosylamino compounds together with unchanged starting material is produced, as a result of which the aminohalogen compounds are mostly obtained in yields of less than 50%. Finally, it is possible to combine a nitrile saponification with the manufacture of the amine or alternatively to prevent a sulphonation, whereas this cannot be avoided when using the corresponding sulphonamides.

However the process described in German Specification 1,205,550 also has disadvantages. Principally there is the risk of an undesired sulphonation, which can only be avoided by using an aluminum chloride melt which is expensive and awkward to handle. Furthermore the process described in the above-mentioned Specification is a two-stage process, inasmuch as the cyclohexylaminoanthraquinones which are to be used as starting substances have in each case to be first manufactured. Finally saponificable groups, for example benzoylamino or nitrile groups are sometimes undesirably saponified under the reaction conditions.

This invention provides a new simpler process for the manufacture of aminoanthraquinones which is free of all these disadvantages. The process according to the invention is characterized by heating an anthraquinone which contains, optionally with other substituents, at least one secondary or tertiary alkylarnino, aralkylamino or cycloalkylamino group or at least one cyclic amino group, in an organic solvent, if desired in the presence of an acid-binding agent and/or of an oxidizing agent, to temperatures above C, if desired under elevated pressure.

Instead of using as the starting product an N-substituted aminoanthraquinone and carrying out the reaction in accordance with the scheme in an organic solvent e.g. nitrobenzene, in the presence or absence of an amine of the formula the manufacture of the aminoanthraquinone can also be carried out and in the same vessel in such a manner that the substituted aminoanthraquinone is only produced as an intermediate in accordance with the scheme In the above formulas A denotes an optionally substituted anthraquinone residue with or without condensed carbocyclic and/or heterocyclic rings, -R denotes a straight chain or branched aliphatic hydrocarbon residue or an araliphatic or cyclophaliphatic hydrocarbon residue, R denotes a hydrogen atom or one of the residues defined under R, and R and R may also together form a cyclic ring, and X denotes a reactive atom or a reactive group for example a nitro, hydroxy, alkoxy or sulpho group or especially a halogen atom.

As residues defined under R there may for example be mentioned those of formula in which B denotes a phenyl or naphthyl residue, n and /R HN by known methods.

As anthraquinones which contain reactive atoms or groups and which may be used as starting products 7 there may for example be mentioned: l-chloro-4- benzoylaminoanthraquinone, l-chloro-S 1-chloro-8- benzoylaminoanthraquinone, l-chloro-3- benzoylaminoanthraquinone, l-chloro- 4aminoanthraquinone, l-cltloro-Z-aminoanthraquinone, I l,4-dichloroanthraquinone, 1,5- dichloroanthraquinone, 1 ,4-dichloro-5- benzoylaminoanthraquinone, 1-chloro-2- cyanoanthraquinone, l-bromo-4-methoxyanthraquinone, l-chloro-4-anilinoanthraquinone, lchloroanthraquinone-6-sulphonic acid, 1 ,5- dinitroanthraquinone, l-chloroanthraquinone. This list can, in accordance with the definition of A-X, be extended as desired.

As amines which are suitable for reaction with the above-mentioned anthraquinon'es, there may for example be mentioned: aliphatic amines having at most 20 carbon atoms in the aliphatic chain, for example n-octadecylamine, n-dodecylamine, n-octylarnine, n-hexylamine, n-butylamine, n-ethylamine, isopropylamine, dodecylamino-propylamine, di-n-octadecylamine, di-noctylamine, diethylamine, hexamethylenediamine; cycloaliphatic amines, for example cyclohexylarnine, cyclooctylamine, N-butyl-cyclohexylamine, amines for example piperidine, pyrrolidine, or morpholine; araliphatic amines for example benzylamine, phenylethylamine and others which correspond to the formula in which A, R and R have the above-mentioned significance and X denotes a reactive atom or a reactive group, optionally in the presence of an acid-binding agent and/or an oxidizing agent, in an organic solventat temperatures above 100 and without isolating the intermediate product of the formula In this connection, soda, N,N-dimethylaniline, aniline, pyridine or an amine of formula may for example be used as the acid-binding agent, and

if desired an oxidizing agent, for example nitrobenzene, m-nitrobenzene sulphonic acid, manganese dioxide, ferric chloride or arsenic acid may also be added. The reaction is carried out in an organic solvent for example nitrobenzene, trichlorobenzene or methylnaphthalene or an excess of the amine used, at temperatures above 100 C, advantageously at the boiling point of the solvent and if required in a closed vessel under elevated pressure, until the reaction mixture cyclic consists essentially of the desired aminoanthraquinone (A-NH2).

The primary aminoanthraquinone is isolated from the reaction mixture by known methods, and the aminoanthraquinone which precipitates after the reaction solution has cooled is generally filtered, optionally recrystallized and washed. The solvent may be separated by distillation, for example steam distillation. The resulting products are valuable starting materials, for example, for the manufacture of dyestuffs, especially vat dyestuffs. They may also be directly used as dyestufls.

In the Examples which follow the parts and percentages, unless otherwise stated, are by weight, and the temperatures are given in degrees centigrade. The melting points are uncorrected.

EXAMPLE 1 18.1 Parts of l-chloro-4-benzoylaminoanthraquinone are stirred for 1 2 hours at 190 with 18.5 parts of dodecylamine (fatty amine C 12, Armeen 12 D of the Armor Industrial Chemical Company) in parts by volume of nitrobenzene. After cooling the precipitate is filtered and recrystallized from a ten-fold quantity of 'ybutyrolactone. The product which crystallizes in small reddish violet needles of melting point 286 is l-amino- 4-benzoylaminoanthraquinone.

EXAMPLE 2 When the 18.5 parts of dodecylamine are replaced by 27 parts of n-octadecylamine or 13 parts of n-octylamine or 11 parts of n-hexylamine or 52 parts of din-octadecylamine or 26 parts of Duomen C of Armor & Company (H N-{CHQ -NH-[CH L CI-I or 10 parts of cyclohexylarnine, l-amino-4- benzoylaminoanthraquinone is similarly obtained.

EXAMPLE 3 EXAMPLE 4 EXAMPLE 5 l l .9 Parts of 1 ,4-dichloro-5- benzoylaminoanthraquinone are stirred for hours at 190 with 22.2 parts of n-dodecylamine in 50 parts by volume of nitrobenzene. After cooling the precipitated 1,4-diamino-5-benzoylaminoanthraquinone can be isolated as a reddish blue powder by filtration.

When the mixture is stirred for only 3 hours at 190 then after cooling, filtering and recrystallization of the residue from butanol a marine blue product is obtained which is 1,4-aminododecylamino-5- benzoylaminoanthraquinone of melting point 171.

EXAMPLE 6 13 Parts of l-chloro-2-aminoanthraquinone and 5 parts of anhydrous sodium acetate are stirred for V4 hour at 185 in 50 parts by volume of benzylamine. After cooling the mixture is poured into water and the precipitate is filtered, dissolved in 1,000 parts by volume of hot ethanol and filtered to clarify. The filtrate is concentrated in vacuo, whereupon l,2- diaminoanthraquinone precipitates in a crystalline form. After filtration and drying about 9 parts of 1,2- diaminoanthraquinone are obtained.

EXAMPLE 7 When in Example 4 the l-chloro-4- benzoylaminoanthraquinone is replaced by the same quantity of l-chloro-5-benzoylaminoanthraquinone, 1- amino-S-benzoylaminoanthraquinone is similarly obtained.

EXAMPLE 8 8.3 Parts of 1,5-dichloroanthraquinone and 11.5 parts of pipen'dine are stirred for 15 hours at 190 in 50 parts by volume of nitrobenzene. After cooling 1,5- diaminoanthraquinone can be isolated from the resinous mass by separation in a silica gel column using chloroform as the eluant.

EXAMPLE 9 10 Parts of 1,5-dinitroanthraquinone and 3.6 parts of benzylamine are stirred for 4 hours at 190 in the presence of 3 parts of sodium bicarbonate in 50 parts by volume of nitrobenzene. After cooling the mixture is filtered, the filtrate is mixed with 750 parts of methanol and the resulting 1-arnino-5-nitroanthraquinone (4 parts) is filtered.

EXAMPLE 10 12.2 Parts of i-chloroanthraquinone and 6 parts of hexamethylenediarnine are stirred in 200 parts of amyl alcohol for 48 hours at under reflux. After cooling the crystalline precipitate is filtered and dried. It consists of a mixture of 1-aminoanthraquinone and l-hexylaminoanthraquinone which can be separated by recrystallization or chromatographically.

EXAMPLE 11 10.8 Parts of 1-chloro-4-benzoylaminoanthraquinone (0.03 mol) are stirred for 15 hours at 190 with 5.6 parts of dodecylamine (0.03 mol) and 2.9 parts of N,N- dimethylaniline (0.03 mol) in 45 parts by volume of nitrobenzene. After cooling 100 parts by volume of methanol are added, the precipitate obtained is filtered and thoroughly washed with hot methanol. About 8 parts of l-amino-4-benzoylaminoanthraquinone are obtained.

10 Parts of l-dodecylamino-4- benzoylaminoanthraquinone are stirred in 50 parts by volume of nitrobenzene for 20 hours at 190. After cooling 10 parts by volume of methanol are added and the precipitate is filtered and washed with methanol. After drying 5.5 parts of l-amino-4- benzoylaminoanthraquinone of melting point 279 are obtained.

The reaction time can be significantly shortened by adding one equivalent of dodecylamine.

EXAMPLE 13 '10 parts of 1-cyclohexylamino-2-methylanthraquinone are stirred in 50 parts by volume of nitrobenzene for 20 hours at l90. After cooling a small amount of methanol is added and the precipitated 1- amino-Z-methylanthraquinone is filtered and washed with methanol and dried. The obtained product has a melting point of 205.

When the l-cyclohexylamino-2-methylanthraquinone is replaced by l-morpholino-2-methylanthraquinone or by l-pyrrolidino-2-methylanthraquinone, 1- amino-Z-methylanthraquinone is likewise obtained.

EXAMPLE 14 17.2 parts of 1-bromo-4-acetylaminoanthraquinone are stirred for 12 hours at with 52.2 parts of di-noctadecylamine in 80 parts by volume of nitrobenzene. After cooling the precipitate is filtered and washed with methanol. 9.5 parts of dried 1-amino-4- acetylaminoanthraquinone are obtained.

When the 52.2 parts of di-n-octadecylamine are replaced by 12.1 parts of a-phenylethylamine or 10.7 parts of benzylamine, l-arnino-4- acetylaminoanthraquinone is likewise obtained in an even better yield.

When the 17.2 acetylaminoanthraquinone of l-bromo-4- replaced by an parts are equimolar amount of 1-bromo-4-thiophen(-2)-carbonylaminoanthraquinone, l-amino-4-thiophencarbonylanthraquinone is obtained.

EXAMPLE 15 10.3 parts of l,4-dichloro-5,8-dihydroxyanthraquinone are treated with 4 parts of benzylamine in 50 parts by volume of nitrobenzene for 15 hours at l85190. After cooling a small amount of methanol is added and the product is filtered off with suction and washed with methanol. After drying about 6.5 parts of l-amino-4- chloro-S,8-dihydroxyanthraquinone are obtained.

When instead of the 4 parts of benzylamine 20 parts are used, both chlorine atoms are replaced and the resulting product is l,4-diamino-5,8-dihydroxyanthraquinone.

The same product is obtained if instead of 1,4- dichloro-S,8-dihydroxyanthraquione an equimolar amount of 1,4-disulfo-5,8-dihydroxyanthraquinone is used. The benzylamine may be replaced by an equimolar amount of a-phenylethylamine, di-n-octylamine, piperidine, pyrrolidine or morpholine.

If the 10.3 parts of 1,4-dichloro-5 ,8-dihydroxyanthraquinone are replaced by 12.8 parts of l-chloro- 4-anilido-5,S-dihydroxyanthraquinone, l-amino-4- anilido-S,8-dihydroxyanthraquinone is obtained in a yield of 75% of the theory.

If the 10.3 parts of 1,4-dichloro-5,8-dihydroxyanthraquinone are replaced by parts of 1,5- dinitroanthraquinone and parts of benzylamine (or an equimolar amount of one of the above-mentioned amines) are used, 1,5-diaminoanthrquinone is ob tained.

lclaim:

l. A process for the manufacture of a primary aaminoanthraquinone which is unsubstituted or substituted by chloro, bromo, nitro, sulfo, hydroxy, amino, lower alkyl, lower alkoxy, aryl or arylamino each containing up to eight carbon atoms, benzoylamino or alkylcarbonylamino containing up to eight carbon atoms, comprising heating, at a temperature above 100 C in an unsubstituted halogenated, alkylated or nitrated aromatic hydrocarbon, or amyl alcohol, an a-secondary or a-tertiary aminoanthraquinone, as defined above, in which the a-amino group is of the formula in which B is a phenyl or naphthyl radical, n and m are integers of at most 20 and p and q are integers of at most 4 and in which R, is a hydrogen atom or R, and wherein R and R together with the nitrogen atom represent pyrrolidino, piperidino or morpholino.

2. A process as claimed in claim 1 wherein n is at least 4, p is 2 or 4, B is a phenyl radical and q is 1 or 2.

3. A process as claimed in claim 1 wherein the asecondary or a-tertiary amino group is dodecylamino, cyclohexylamino, morpholino or pyrrolidino.

4. A process as claimed in claim 1 wherein the inert organic solvent is an unsubstituted, halogenated, alkylated or nitrated aromatic hydrocarbon.

5. A process as claimed in claim 1 wherein nitrobenzene is used as the inert organic solvent.

6. A process as claimed in claim 1 wherein said heating is from the boiling point of the solvent.

7. A process as claimed in claim 1 wherein said heating is at the reflux temperature of the solvent.

8. A process for the manufacture of a primary aaminoanthraquinone which is unsubstituted or substituted by chloro, bromo, nitro, sulfo, hydroxy, amino, lower alkyl, lower alkoxy, aryl or arylamino each containing up to eight carbon atoms, benzoylamino or alkylcarbonylamino containing up to eight carbon atoms, comprising heating at a temperature above 100 C in an unsubstituted, halogenated, alkylated, or nitrated aromatic hydrocarbon, or amyl alcohol, an a-anthraquinone, which is unsubstituted or substituted by chloro, bromo, nitro, sulfo, hydroxy, amino, lower alkyl, lower alkoxy, aryl or arylamino each containing up to eight carbon atoms, benzoylamino or alkylcarbonylamino containing up to eight carbon atoms, and in which the a-position contains a nitro, hydroxy, alkoxy, sulfo or halogen atom in the presence of a secondary or tertiary in or a naphthyl radical, n and m are integers of at most 20 and p and q are integers of at most 4 and in which R, is a hydrogen atom or R, and wherein R and R together with the nitrogen atom represent pyrrolidino, piperidino or morpholino.

9. A process as claimed in claim 8 wherein n is at least 4, p is 2 or 4, B is a phenyl radical and q is 1 or 2.

10. A process as claimed in claim 8 wherein the secondary or tertiary amine is an alkyl or dialkylamine of 6-18 carbon atoms, cyclohexylamine, benzylamine, a-phenethylamine, hexamethylenediamine, piperidine, pyrrolidine or morpholine.

11. A process as claimed in claim 8 wherein said heating is from l35200 C.

12. A process as claimed in claim 8 wherein the inert organic solvent is an unsubstituted, halogenated, alkylated or nitrated aromatic hydrocarbon.

13. A process as claimed in claim 8 wherein nitrobenzene is used as the inert organic solvent.

14. A process as claimed in claim 8 wherein said heating is at reflux temperature.

15. A process as clainieii in claim 8 wherein said I heating is carried out in the presence of a agent.

n acid-binding *zgz g UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated October 24, 1972 Patent No. 3,7 ,7

Inventor-(s) Hans Altermatt 7 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 8, line 47, after "in" insert which B is a phenyl Signed and sealed this 16th day of April 19%..

(SEAL) Attest: r

EDWARD PLFLETOI-IERJR; c. MARSHALL DANN Attesting Officer Commissioner of Patents 

2. A process as claimed in claim 1 wherein n is at least 4, p is 2 or 4, B is a phenyl radical and q is 1 or
 2. 3. A process as claimed in claim 1 wherein the Alpha -secondary or Alpha -tertiary amino group is dodecylamino, cyclohexylamino, morpholino or pyrrolidino.
 4. A process as claimed in claim 1 wherein the inert organic solvent is an unsubstituted, halogenated, alkylated or nitrated aromatic hydrocarbon.
 5. A process as claimed in claim 1 wherein nitrobenzene is used as the inert organic solvent.
 6. A process as claimed in claim 1 wherein said heating is from 100* the boiling point of the solvent.
 7. A process as claimed in claim 1 wherein said heating is at the reflux temperature of the solvent.
 8. A process for the manufacture of a primary Alpha -aminoanthraquinone which is unsubstituted or substituted by chloro, bromo, nitro, sulfo, hydroxy, amino, lower alkyl, lower alkoxy, aryl or arylamino each containing up to eight carbon atoms, benzoylamino or alkylcarbonylamino containing up to eight carbon atoms, comprising heating at a temperature above 100* C in an unsubstituted, halogenated, alkylated, or nitrated aromatic hydrocarbon, or amyl alcohol, an Alpha -anthraquinone, which is unsubstituted or substituted by chloro, bromo, nitro, sulfo, hydroxy, amino, lower alkyl, lower alkoxy, aryl or arylamino each containing up to eight carbon atoms, benzoylamino or alkylcarbonylamino containing up to eight carbon atoms, and in which the Alpha -position contains a nitro, hydroxy, alkoxy, sulfo or halogen atom in the presence of a secondary or tertiary amine of the formula in which R is CH3-(CH2)n 1-, H-(CH2)n 1-HN-(CH2)m-,B-(CH2)q- or in or a naphthyl radical, n and m are integers of at most 20 and p and q are integers of at most 4 and in which R1 is a hydrogen atom or R, and wherein R and R1 together with the nitrogen atom represent pyrrolidino, piperidino or morpholino.
 9. A process as claimed in claim 8 wherein n is at least 4, p is 2 or 4, B is a phenyl radical and q is 1 or
 2. 10. A process as claimed in claim 8 wherein the secondary or tertiary amine is an alkyl or dialkylamine of 6-18 carbon atoms, cyclohexylamine, benzylamine, Alpha -phenethylamine, hexamethylenediamine, piperidine, pyrrolidine or morpholine.
 11. A process as claimed in claim 8 wherein said heating is from 135*-200* C.
 12. A process as claimed in claim 8 wherein the inert organic solvent is an unsubstituted, halogenated, alkylated or nitrated aromatic hydrocarbon.
 13. A process as claimed in claim 8 wherein nitrobenzene is used as the inert organic solvent.
 14. A process as claimed in claim 8 wherein said heating is at reflux temperature.
 15. A process as claimed in claim 8 wherein said heating is carried out in the presence of an acid-binding agent. 